EP0004942B1 - Process for the manufacture of alkylene carbonates - Google Patents

Process for the manufacture of alkylene carbonates Download PDF

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Publication number
EP0004942B1
EP0004942B1 EP79101116A EP79101116A EP0004942B1 EP 0004942 B1 EP0004942 B1 EP 0004942B1 EP 79101116 A EP79101116 A EP 79101116A EP 79101116 A EP79101116 A EP 79101116A EP 0004942 B1 EP0004942 B1 EP 0004942B1
Authority
EP
European Patent Office
Prior art keywords
process according
bicarbonate
synthesis
halohydrin
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79101116A
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German (de)
English (en)
French (fr)
Other versions
EP0004942A1 (en
Inventor
Carlo Dr. Chem. Venturello
Rino D'aloisio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ECP Enichem Polimeri SRL
Original Assignee
Montedison SpA
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Filing date
Publication date
Application filed by Montedison SpA filed Critical Montedison SpA
Publication of EP0004942A1 publication Critical patent/EP0004942A1/en
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Publication of EP0004942B1 publication Critical patent/EP0004942B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates

Definitions

  • This invention relates to a process for the manufacture of alkylene carbonates and particularly of alkylene carbonates having 2 to 4 carbon atoms in the alkylene chain.
  • alkylene carbonates and in particular ethylene carbonate and propylene carbonate, have great utility for instance as solvents of organic polymers, as electrochemical solvents, and as synthesis intermediates.
  • Processes for manufacturing alkylene carbonates are already well known.
  • One such method involves the reaction of an epoxide with carbon dioxide in the presence of proper catalysts.
  • Another method is based on the reaction between vicinal glycols and phosgene.
  • Still another method is based on the reaction between vicinal halohydrins and sodium bicarbonate in the presence of carbon dioxide.
  • the invention relates to a process for the manufacture of alkylene carbonates, and particularly alkylene carbonates having from 2 to 4 carbon atoms in the alkylene chain, starting from a corresponding vicinal halohydrin, having the general formula: in which R s , R b , R c , and R d , which can be similar or dissimilar to each other, are hydrogen or alkyl, aryl, alkylaryl or arylalkyl radicals, and X is a halogen, wherein said halohydrin is reacted with the bicarbonate of a quaternary ammonium compound, the amount of which - expressed as NR 4 groups (R 4 being the 4 substituents of the ammonium compound) - is equivalent or slightly in excess over the amount of the halohydrin (expressed in molar terms).
  • high yields may be obtained without any appreciable formation of glycols in very short times and at room temperatures and pressures by using bicarbonates of quaternary ammonium cations, such as, for example, tetramethyl-ammonium bicarbonate, tetraethylammonium bicarbonate, tetra-n-butyl-ammonium bicarbonate, benzyl-trimethyl-ammonium bicarbonate.
  • Similar results have been achieved by using strongly basic anionic resins having quaternary ammonium terminals or end groups (in the form of hydroxyls), carbonated with C0 2 before the synthesis.
  • KASTEL® A 300 P examples of the latter are the products commercially known as KASTELS A 300, KASTEL® A 300 P, KASTEL ® A 500, KASTEL O A 500 P, AMBERLITE® IRA ⁇ 400 ⁇ OH, KASTELO A 501 D, KASTEL® A 510, and the like.
  • terminal or end groups of strongly basic quaternary resins to be used according to this invention may be, for instance, of the type
  • halohydrins means in particular chlorohydrins, bromohydrins and iodohydrins. Examples are the following halohydrins: ethylene chlorohydrin, ethylene bromohydrin, ethylene iodohydrin, 2-chloro-propanol-1, 1-chloro-propanol-2, 2-bromo-propanol-1, 1-bromo-propanol-2, 2-iodo-propanol-1, 1-iodo-propanol-2, 2-chloro-butanol-1, 2-bromo-butanol-1, 2-iodo-butanol-1, erythro-3-bromo-butanol-2, threo-3-bromo-butanol-2, and mixtures thereof.
  • solvents may be employed for the synthesis according to this invention, such as for example methanol, n-butanol, acetone, dioxane, acetonitrile, dimethylformamide, benzene, toluene, xylols, dimethylsulphoxide, and the like.
  • acetonitrile has been used with excellent results.
  • aqueous-organic mixtures such as water-dioxane, water-acetonitrile, and the like, may also be employed as solvent. In some particular cases even water alone may be used.
  • the amount of ammonium compound, expressed as NR4 groups, must be equivalent to or slightly in excess - in molar terms - with respect to the amount of halohydrin employed.
  • ammonium compound is present in the form of a halide, according to the reaction scheme: wherein the symbols have the meanings specified above.
  • the tetralkylammonium halide or the resin halide may be easily separated from the reaction mixture by filtration and recovered nearly quantitatively.
  • the filtrate can be fractionated to give the required alkylene carbonate.
  • the resin when using an anion exchange resin, the resin is regenerated "in situ" after conclusion of the reaction, for which it may be advisable to work with two or more reactors in parallel, preferably of the suspended bed type, running alternately. While one reactor works, the other is shut down and the resin is regenerated, for instance by means of dilute aqueous NaOH of NH 4 0H solutions and successive carbonation with CO 2 ,
  • the synthesis temperature may vary over a wide range. Although excellent results are obtained at room temperature or even as low as 0°C, a temperature increase may be useful in some cases for substantially reducing the reaction period. Of course, the reaction temperature must not exceed either the boiling point of the solvent or the degradation point of the exchange resin. Thus, temperatures between 0 to 100°C or 20°C to the boiling point of the solvent are useful.
  • the influence exerted by the carbon dioxide pressure is not critical. Nevertheless, when operating at higher temperatures than room temperature, an increase of the C0 2 pressure is particularly advantageous. In principle, it is useful to operate between room pressure and 10000 Kilopascal (kPa), and preferably between room pressure and 3000 kPa.
  • the filter cake was washed with 50 cm 3 of acetonitrile, the acetonitrile washings were then added to the filtered solution, and the whole was distilled under vacuum to recover the solvent.
  • the residual liquid was diluted with acetone and 1.5 g of salt still contained therein were separated by filtration. The acetone was evaporated, and the oil contained therein was distilled under vacuum (10.1 g).
  • Example 3 was repeated using threo-3-bromo-butanol-2 as reagent.
  • the reaction time was 60 minutes.
  • Example 3 was repeated using 2-bromo-1-phenyl-ethanol as reagent and adjusting the reaction time to about 15 minutes. 16.57 g of a yellowish residual oil were obtained, which solidified at room temperature.
  • Example 3 was repeated using butylene bromohydrin as reagent and adjusting the reaction time to about 15 minutes. 12.6 g of a residual oil were obtained, which, after distillation under vacuum (68°-70°C/0,53-0,65 mbar), provided 11.2 g of butylene carbonate (at 99% purity) in the form of a colorless oil with a yield of about 96.4%.
  • Example 2 was repeated using benzyl-trimethylammonium bicarbonate as ammonium reagent. 8.59 g of propylene carbonate of 98.5% purity were obtained. The yield was about 85.48%.
  • Example 8 was repeated contacting 0.01 mole of propylene iodohydrin with 7.5 g of a weakly basic anion exchange resin, commercially known as KASTEL* A-101, suspended in 16 cm 3 of a mixture containing water and dioxane in equal parts. The suspension was maintained under stirring at room temperature and in a carbon dioxide atmosphere for 4 hours, thereby obtaining 0.41 g of propylene carbonate (gas-liquid chromatographic analysis), corresponding to a yield of 40%.
  • a weakly basic anion exchange resin commercially known as KASTEL* A-101
  • Example 9 was repeated contacting in an autoclave and under stirring 0.04 moles of propylene iodohydrin with 30 g of a weakly basic resin (KASTEL® A ⁇ 101), suspended in 64 cm 3 of a mixture containing water and dioxane in equal parts.
  • a weakly basic resin KASTEL® A ⁇ 101
  • Example 6 0.01 mole of butylene chlorohydrin was added to a suspension of 0.012 moles of tetramethylammonium bicarbonate in 25 cm 3 of acetonitrile, whereupon the procedure of Example 6 was repeated.
  • Example 12 was repeated using propylene iodohydrin. The mixture was maintained at 60°C under CO 2 pressure (3000 kPa) for 30 minutes. The conversion of the iodohydrin to propylene carbonate was practically complete.
  • Example 12 was repeated using, as a strongly basic resin, KASTEL ® A-300 in the hydroxylated form.
  • the resin in question was one having quaternary terminal groups of the type on a matrix obtained by copolymerizing styrene and divinylbenzene.
  • Example 14 was repeated using water as the carbonation solvent for resin KASTEL ⁇ A-300--OH and as the reaction solvent. The mixture was kept at 60°C under C0 2 pressure (2200 kPa) for 1.5 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP79101116A 1978-04-14 1979-04-11 Process for the manufacture of alkylene carbonates Expired EP0004942B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2232378 1978-04-14
IT22323/78A IT1095606B (it) 1978-04-14 1978-04-14 Processo per la sintesi di alchilencarbonati

Publications (2)

Publication Number Publication Date
EP0004942A1 EP0004942A1 (en) 1979-10-31
EP0004942B1 true EP0004942B1 (en) 1982-12-22

Family

ID=11194664

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79101116A Expired EP0004942B1 (en) 1978-04-14 1979-04-11 Process for the manufacture of alkylene carbonates

Country Status (8)

Country Link
US (1) US4226778A (ja)
EP (1) EP0004942B1 (ja)
JP (1) JPS55367A (ja)
CA (1) CA1113947A (ja)
DE (1) DE2964339D1 (ja)
ES (1) ES479522A1 (ja)
IT (1) IT1095606B (ja)
SU (1) SU812179A3 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4129752A1 (de) * 1991-09-04 1993-03-11 Dainippon Ink & Chemicals Verfahren zur herstellung von 2-oxo-1,3-dioxolanen

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325874A (en) * 1981-05-26 1982-04-20 The Halcon Sd Group, Inc. Process for producing alkylene carbonates
US4483994A (en) * 1983-02-22 1984-11-20 The Halcon Sd Group, Inc. Process for the production of alkylene carbonates and oxides
US4931571A (en) * 1984-10-25 1990-06-05 Scientific Design Company, Inc. Process for preparing alkylene carbonates from alkylene oxides
US4851555A (en) * 1984-10-25 1989-07-25 Scientific Design Company, Inc. Process for preparing alkylene oxides from alkylene carbonates
DE3529263A1 (de) * 1985-08-16 1987-02-19 Hoechst Ag Verfahren zur herstellung von 2-oxo-1,3-dioxolanen
DE3723782A1 (de) * 1987-07-16 1989-01-26 Dainippon Ink & Chemicals Verfahren zur herstellung von cyclocarbonatverbindungen
ZA98901B (en) * 1997-02-07 1998-08-17 Shell Int Research Process for the manufacture of epoxy compounds
US6258962B1 (en) 1999-06-14 2001-07-10 Mobil Oil Corp. Process for producing alkylene carbonates
US6573396B2 (en) 2001-10-12 2003-06-03 Exxonmobil Chemical Patents Inc. Co-production of dialkyl carbonates and diols with treatment of hydroxy alkyl carbonate
US6620959B1 (en) 2002-04-16 2003-09-16 Exxonmobil Chemical Patents Inc. Process for the production of unsymmetric and/or symmetric dialkyl carbonates and diols
US20080214386A1 (en) * 2004-03-01 2008-09-04 Toshikazu Takahashi Catalyst for Cyclic Carbonate Synthesis
JP4811758B2 (ja) * 2005-07-19 2011-11-09 独立行政法人産業技術総合研究所 イオン性液体を反応媒体として用いるアルキレンカーボネートの製造方法
WO2014171894A1 (en) * 2013-04-18 2014-10-23 Agency For Science, Technology And Research Synthesis of cyclic carbonates
TWI636980B (zh) * 2013-07-19 2018-10-01 獨立行政法人產業技術綜合研究所 Method for producing cyclic carbonate
CN114478187B (zh) * 2022-02-21 2023-01-31 福州大学 一种反应精馏联产甲醇和碳酸乙烯酯的工艺
KR20230139820A (ko) * 2022-03-22 2023-10-06 서울대학교산학협력단 알킬렌 카보네이트의 합성 방법

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1907891A (en) * 1928-11-14 1933-05-09 Ig Farbenindustrie Ag Production of carbonic acid esters of the glycols
US2873282A (en) * 1952-04-05 1959-02-10 Jefferson Chem Co Inc Catalytic process for producing alkylene carbonates
US2766258A (en) * 1952-05-15 1956-10-09 Jefferson Chem Co Inc Process for isolation of alkylene carbonates
US2766285A (en) * 1952-10-20 1956-10-09 Lilly Co Eli Substituted aminopropynes and process for their preparation
US2773070A (en) * 1952-10-31 1956-12-04 Jefferson Chem Co Inc Catalytic process for producing alkylene carbonates
US2784201A (en) * 1953-08-11 1957-03-05 Union Carbide & Carbon Corp Process of making alkylene carbonates
US3025305A (en) * 1959-04-21 1962-03-13 Sinclair Refining Co Cyclic carbonate from olefin
US3535342A (en) * 1968-02-07 1970-10-20 Dow Chemical Co Process for making alkylene carbonates
US3923842A (en) * 1974-06-28 1975-12-02 Phillips Petroleum Co Preparation of oxirane compound from the corresponding olefin via the cyclic carbonate ester
IT1022442B (it) * 1974-09-30 1978-03-20 Montedison Spa Procedimento per la preparazione di alchilencarbonati

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4129752A1 (de) * 1991-09-04 1993-03-11 Dainippon Ink & Chemicals Verfahren zur herstellung von 2-oxo-1,3-dioxolanen

Also Published As

Publication number Publication date
JPS6247182B2 (ja) 1987-10-06
IT7822323A0 (it) 1978-04-14
US4226778A (en) 1980-10-07
CA1113947A (en) 1981-12-08
SU812179A3 (ru) 1981-03-07
JPS55367A (en) 1980-01-05
DE2964339D1 (en) 1983-01-27
EP0004942A1 (en) 1979-10-31
ES479522A1 (es) 1980-01-16
IT1095606B (it) 1985-08-10

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